Certain 2,2-dimethyl-propanal-carbamoyloximes fungicides

ABSTRACT

WHEREIN R1 represents C1-C4 alkyl, C2-C4 alkenyl or phenyl and R2 represents C1-C4 alkyl, processes for their production and their use for pest control.   2,2-Dimethyl-propanal-carbamoyloximes of the formula

United States Patent Kristiansen Mar. 25, 1975 CERTAIN2,2-DIMETHYL-PROPANAL- CARBAMOYLOXIMES FUNGICIDES [75] Inventor: OddKristiansen.Reinach/ Basella nd switzgrland [73] Assignee: Ciba-GeigyCorporation, Ardsley,

22 Filed: May 2,1974

21 Appl.No.:466,330

Related US. Application Data [62] Division of Ser. No. 322,584, Jan. 10,1973, Pat. No. 3,822,359, which is a division of Ser. N0. 198,420, NOV.12, 1971, Pat. NO. 3,718,683.

UNITED STATES PATENTS 3,270,054 8/1966 Gogneux ct al 260/456 3,674,8297/1972 Arlt 260/456 Primary E.\aminer-Vincent D. Turner Attorney, Agent,or FirmFrederick H. Rabin [57] ABSTRACT2,2-Dimethyl-propanal-carbamoyloximes of the formula wherein Rrepresents C -C alkyl, C C alkenyl or phenyl and R represents C C alkyl,processes for their production and their use for pest control.

13 Claims, N0 Drawings CERTAIN 2,2-DIMETHYL-PROPANAL- CARBAMOYLOXIMESFUNGICIDES This is a division of application Ser. No. 322,584, filedJan. 10, 1973, now U.S. Pat. No. 3,822,359 which in turn is a divisionof application Ser. No. 198,420, filed on Nov. 12, 1971, now US. Pat.No. 3,718,683.

The present invention relates to new 2,2-dimethyl Ipropanal-carbamoyloxime derivatives, to processes for the productionthereof, and to the use of these derivatives for pest control.

The new 2,2-dimethyl-propanol-carbamoyloximes have the followingformula:

R represents C -C alkyl.

The C C, alkyl groups and (I alkenyl groups which are concernedaccording to the invention can be straight-chain or branched,substituted or unsubstituted. Substituents are preferably halogens suchas fluorine, chlorine, bromine and/or iodine, preferably fluorine and/orchlorine.

The phenyl denoted by R can be substituted or unsubstituted. Examples ofSubstituents on the phenyl nucleus are: halogen such as fluoringe.chlorine, bromine and/or iodine, preferably chlorine, N and/or C -Calkyl, preferably methyl. Examples of C -C alkyl groups or C C, alkenylgroups are, amongst others,: methyl, ethyl, (n)-propyl, isopropyl, (n)-,(i)-, (sec.)-, (tert.)-butyl, CF CCl CH Cl, Allyl, 3,3,3-trichloropropene.

Compounds preferred because ofthe effect they produce are compounds offormula I wherein R represent methyl, chloromethyl, ethyl, (n)-propyl,(n)-butyl,-

3,3,3trichloropropene, 4-rnethylphenyl and 2,4,5-'

trichlorophenyl, and R represents methyl or ethyl.

Particularly preferred are, however, compounds of formula I wherein Rrepresents chloromethyl, ethyl or (n)-propyl, and R represents methyl orethyl.

Examples of such compounds are:

3-( 4 -methylphenylsulphonyloxy )-2,2-dimethylpropanal-( N'-methylearbamoyl )-oxirne,

3-( methylsulphonyloxy )-2 ,Z-dimethyl-propanal-(Nmethylcarbamoyl)-oxime,

3-(chloromethylsulphonyloxy)-2,2-dimethyl-propanal- (N '-methylcarbamoyl)-oxime,

3( 2 ,4 ,5 -trichlorophenylsulphonyloxy )-2,2-dimethylpr0panol-( N-methylcarbamoyl )-oxime, 3-( 3 ,3 ,3 -trichloropropenesulphonyloxy)-2,2-

dimethyl-propanol-( N -methylcarbamoyl)-oxime, 3-( n-propylsulphonyloxy)-2,2-dimethyl-propanal-( N methylcarbamoyl)-oxime,

3-( n-butylsulphonyloxy)-2,2-dimethyl-propanol-( Nmethylcarbamoyl)-oxime,

3-( ethylsulphonyloxy)-2,2-dimethyl-propanal-( N methycarbamoyl)-oxime,

3-( ethylsulphonyloxy)-2 ,2-dimethyl-propanal-( N ethylcarbamoyl)-oxime,

.3-( chloromethylsulphonyloxy )-2,2-dimethyl-propanal- (N-ethylcarbamoyl)-oxime.

The compounds of formula I are produced by reacting2-hydroxy-2,Z-dimethylpropaldehyde of the formula:

HOCH2C-CHO (II) CH I in air tanner known per se, to give the 65156;convert ing this with a alkali isocyanate of the formula:

R NCO (lll) to a carbamoyloxime of the formula:

Y B HOoh2C--CH NO-%3NHR (IV); 0 CH and then reacting this, in thepresence of an acidbinding agent, with a sulphochloride of the formula:

in the formulae H to V, R and R have the meanings given for the formulaI.

Suitable acid-binding agents are tertiary amines, e.g. trialkylamines,pyridine, pyridine bases, dialkylanilines, etc.; also inorganic basessuch as hydrides, hydroxides and carbonates of alkali metals andalkaline-earth metals. In the case of the reaction with an isocyanate offormula [11, it is advisable in some cases to employ catalysts, such as,e.g. tertiary amines or organo-tin compounds.

The described process is performed in solvents or diluents inert to thereactants. Suitable in this respect are, e.g. ethers and etherealcompounds such as diethyl ether, dipropyl ether, dioxane,tetrahydrofuran; amides such as N,N-dialkylated carboxylic acid amides;aliphatic, aromatic, as well as halogenated hydrocarbons, especiallybenzene, toluene, xylene, chloroform, chlorobenzene, etc.; nitriles suchas acetonitrile, etc.. For the production of the oxime, water and alsomixtures of alkanols with water are preferred. The reaction temperaturesfor the production of the oxime are 2()-l00, for that of thecarbamoyloxime: 0-50,preferably l5-35, and for that of thesulphonyloxycarbamoyloxime: 20-80.

It is known that oximes can be present in two stereoisomeric forms,namely the synand anti-form. Also the2,2-dimethyl-propanal-carbamoyloxime derivatives of formula I exist inthese two forms. Accordingly, the expression2,2-dimethyl-propanal-carbamoyloxime derivatives of formula I relates toboth stereoisomeric forms in the context of the present invention.

The starting material of formula ll for the reactions according to theinvention is known. The carbamoyloximes of formula IV which are obtainedas intermediate products have not been described hitherto.

The active substances of formula I are suitable for the control of themost diverse pests on animals and plants.

The active substances are effective, in particular, against alldevelopment stages, such as, e.g. eggs, larvae, nymphs, pupae and adultsof insects and members of the order acarina, such as mites and ticks.

The compounds of formula I can be used, for example, against thefollowing insects, or members of the order acarina: Insects of thefamilies: Teltigonidae; Gryllidae; Gryilotalpidae; Blattidae;Peduviidae; Phyyhocoriae; Cimicidae; Delphacidae; Aphididae;Diaspididae; Pseudococcidae; Scarabaeidae; Dermestidae: Coccinellidae;Tenebrionidae; Chrysomelidae; Bruchidae; Tineidae; Noctindae;Lymatriidae; Pyralidae; Culicidae; Tipulidae; Stomoxydae; Trypetidae;Muscidae; Calliphoridae and Pulicidae; as well as acarida of thefamilies: lxodidae; Argasidae; Tetranychidae and Dermanyssidae.

The insecticidal or acaricidal action can be substantially broadened andadapted to suit the given conditions by the addition of otherinsecticides and/or acaricides.

Suitable additives are, amongst others, eg the following activesubstances:

Bis-0,0-diethylphosphoric acid anhydride (TEPP) Dimethyl-( 2,2,2-trichlorol -hydroxyethyl)- phosphonate (TRICHLORFON)l,2-dibromo-2,2-dichloroethyldimethylphosphate (N ALED)2,2-dichlorovinyldimethylphosphate (DICHLORVOS)Z-methoxycarbamyl-l-methylvinyldimethylphosphate (MEVINPHOS) Dimethyll-methyl-2-(methylcarbamoyl)- vinylphosphate cis (MONOCROTOPHOS)3-dimethoxyphosphinyloxy )-N,N-dimethyl-ciscrotonamide (DICROTOPHOS)2-chloro-2-diethylcarbamoyll -methylvinyldimethylphosphate(PHOSPHAMIDON) 0,0-diethyl-(or S)-2-(ethylthio)-ethylthiophosphate(DEMETON) S-ethylthioethyl-0,0-dimethyl-dithiophosphate OMETON)0,0-diethyl-S-ethylmercaptomethyldithiophosphate (PHORATE)0,0-diethyl-S-2-ethylthio)ethyldithiophosphate SULFOTON)0,0-dimethyl-S-2-(ethylsulphinyl)ethylthiophosphate (OXYDEMETONMETl-IYL)0,0-dimethyl-S-( l ,2-dicarbethoxyethyldithiophosphate (MALATHION) 0,0,0 ,O-tetraethyl-S,S '-methylene-bis-dithiophosphate (ETHION)O-ethyl-S,S'-dipropyldithiophosphate 0,0-dimethyl-S-(N-methyl-N-formylcarbamoylmethyl)-dithioph0sphate MOTHION)0,0-dimethyl-S-(N-methylcarbamoylmethyl)dithiophosphate (DIMETHOATE)(THI- (FOR- 0,0-dimethyl-O-p-nitrophenylthiophosphate (PA-RATHION-METHYL) 0,0-diethyl-0-p-nitrophenylthiphosphate (PARA- THION) 4O-ethyl-O-p-nitrophenylphenylthiophosphate (EPN)0,0-dimethyl-0-(4-nitro-m-tolyl)thiophosphate (FENl- TROTHION0,0-dimethyl-O-2,4-5-trichlorphenylthiophosphate (RONN EL)O-ethyl-O,2,4,5-trichl0rphenylethylthiophosphate (TRICHLORONATE)0,0-dimethyl-0-2,5-dichlor-4-bromphenylthiophosphate BROMOPHOS)0,0-dimethyl-0-( 2,5-dichl0r4-jodphenyl)- thiophosphate (JODOFENPHOS)4-tert. butyl-2-chlorphenyl-N-methyl-O- methylamidophosphate (CRUFOMATE)0,0-dimethyl-O-( 3-methyl-4- methylmercaptophenyl )thiophosphate( FENTHION lsopropy-lamino-O-ethyl-0-(4-methylmercapto-3- methylphenyl)-phosphate 0,0-diethyl-0-p-(methylsulphinyl)phenylthioph0sphate(FENSUTFOTHION) 0-p-( dimethylsulfamido )phenyl0,0-dimethylthiophosphate(FAMPHUR)0,0,0,O-tetramethyl-0,0'-thiodi-p-phenylenthiophosphateO-ethyl-S-henyi-ethyldithiophosphonate 0,0-dimethyl-O-(a-methylbenzyl-3-hydroxycrotonyl phosphate Z-chlorl2,4-dichlorphenyl)vinyl-diethylphosphate( CHLORFENVINPHCS)2-chlor-1-(2,4,5-trichlorphenyl)vinyldimethylphosphate O-[ 2-chlorl2,5-dichlorphenyl) ]vinyl-0,0-diethylthiophosphatePhenylglyoxylonitriloxim-0,0-diethylthiophosphate (PHOXIM)0,0-diethyl-0-( 3-chlor-4-methyl-2-0Xo-2-H- lbenzopyran-7-yl)-thiophosphate (COUMAPHOS)2,3-p-dioxandithi0l-S,S-bis(0,0-diethyldithiophosphate (DIOXATHION) 5-[6-chlor-2-ox0-3-benzoxazolinyl )methyl ](),0-diethyldi'thio-phosphate(PHOSALON E) 2-(diethoxyphosphinylimino l ,3-dithiolane0,0-dimethyl-S-[Z-methoxyl ,3,4-thiadiazol-5-( 4H onyl-( 4)-methyl]dithiophosphate0,0-dimethyl-S-phthalimidomethyl-dithiophosphate (IMIDAN)0,0-diethyl-O-( 3 ,5 ,6-trichlor-2-pyridyl )thiophosphate0,0-diethyl-O-2-pyrazinylthiophosphate THlONA- ZlN) 0,0-diethyl-0-(2-is0propyl-4-methyl-6-pyrimidyl )thiophosphate DIAZINON)0,0-diethyl-O-( 2-chinoxalyl )thiophosphate 0,0-dimethyl-S-(4-oxo-l,2,3-benzotriazin-3(4H ylmethyl)-dithiophosphate (AZINPHOSMETHYL)0,0-diethyl-S-( 4-oxol ,2 ,3-benzotriazin-3 4H ylmethyl)-dithiophosphate(AZINPHOSETHYL) S-[(4,6-diamino-s-triazin-2-yl)methyl]-0,0-dimethyldithiophosphate (MENAZON) 0,0-dimethyl-O-(3-chlor-4-nitrophenyl )thiophosphate (CHLORTHION) 0,0-dimethyl-0( or S)-2-(ethylthioethyl)thiophosphate (DEMETON-S-METHYL)2-(0,0-dimethy1-phosphoryl-thiomethyl)-5-methoxypyrone-4-3,4-dichlorbenzyl-triphenylphosphonium chloride0,0-diethyl-S-( 2,5-dichlorphenylthiomethyl dithiophosphate (PHENKAPTON)0,0-diethyl-O-( 4-methyl-coumarinyl-7 )-thiophosphate (POTASAN) 55-amino-bis(climethylamido)phosphinyl-3-phenyl- 1,2,4-triazole(TRIAMIPI-IOS) N-methyl-5-(0,0-dimethylthiolphosphoryl)-3-thiavaleramide(VAMlDOTI-IION) 0,0-diethyl--[2-dimethylamino-4-methylpyrimidyl-(6)1-thiophosphate (DIOCTHYL) 0,0-dimethyl-S-(methylcarbamoylmethyl)-thiophosphate (OMETHOATE) O-ethyl-O-(S-quinolinyl)-phenylthiophosphonate(OX- INOTHIOPI-IOS) O-methyl-S-methyl-amidothiophosphate (MONITOR)0-methyl-0-(2,5-dichlor-4-bromphenyl)-benzothiophosphate (PI-IOSVEL).

CARBAMIC ACID DERIVATIVES l-naphthyl-N-methylcarbamate (CARBARYL)butinyl-4-chlorophenylcarbamate4-dimethylamino-3-tolyl-N-methylcarbamate (AMINOCARB)4-methylthio-3,5-xylyl-N-methylcarbamate (METI-Il- OCARB)2-chlorophenyl-N-methylcarbamate (CPMC)l-(dimethylcarbamoyl)-5-methyl-3-pyrazolyl-N,N-

dimethylcarbamate (DIMETHILAN)2,3-dihydro-2,2-dimethyl-7-benzofuranyl-N- methylcarbamate (CARBOFURAN)2-methyl-2-methylthiopropionaldehyde-O-(methylcarbamoyl)-oxime(ALDICARB) 8-quinaldyl-N-methylcarbamate and salts thereof3-isopropyl-5-methylphenyl-N-methylcarbamate (PROMECARB) 2-(l,3-dioxolan-2-yl)-phenyl-N-methylcarbamate (DI- OXACARB)2-(4,5-dimethyl-1,3-dioxalan-2-yl)-phenyl-N- methylcarbamate 2( I,3-dithiolan2-yl)-phenyl-N-methylcarbamate 2-(l,3-dithiolan-2-yl)phenyl-N,N-dimethylcarbamate2-isopropoxyphenyl-N-methylcarbamate (APROCARB)4-diallylamino-3,S-xylyl-N-methylcarbamate LYXICARB)l-isopropyl-3-methylpyrazol-5-yl-N,N-dimethylcarbamate (ISOLAN)l-methylthioethylimino-N-methylcarbamate THOMYL)2-[propargylethylamino]-phenyl-N-methylcarbamateZ-[propargylmethylamino]-phenyl-N- methylcarbamateZ-[dipropargylamino]-phenyl-N-methylcarbamate3-methyl-4-[dipropargylamino]-phenyl-N- methylcarbamate3,5-dimethyl-4-[dipropargylamino]-phenyl-N- methylcarbamate2-[allylisopropylamino]-phenyl-N-methylcarbamate NITROPHENOLS ANDDERIVATIVES 4,6-dinitro-6-methylphenol, Na-salt [Dinitrocresol]dinitrobutylphenol-( 2,2 ',2 "-triethanolamine saltcyclohexyl-4,6-dinitrophenol [Dinex] 2-(1-methylheptyl)-4,-dinitrophenyl-crotonate [Dinocap]2-sec.-butyl-4,6-dinitrophenyl-3-methyl-butenoate [Binapacryl]2-sec.-butyl-4,6-dinitrophenyl-cyclopropionate2-sec.-butyl-4,6-dinitrophenylisopropylcarbonate [Dinobuton] Oomycetes,

MISCELLANEOUS pyrethin I pyrethin II3-allyl-2-methyl-4-oxo-2-cyclopentenl -ylchrysanthemumate (Allethrin)6-chloriperonyl-chrysanthemumate (Barthrin)2,4-dimethylbenzyl-chrysanthemumate (Dimethrin)2,3,4,5-tetrahydrophthalimidomethylchrysanthemumate4-chlorobenzyl-4-chlorophenylsulphide [Chlorbensid]6-methyl-2-oxo-l,3-dithiolo-[4,5-b]-quinoxaline [Quinomethionate](I)-3-(Z-furfuryl)-2-methyl-4-oxocyclopent-2-enyl(I)- (cistrans)-chrysanthemum'monocarboxylate [Furethrin] 2-pivaloyl-indane- I,3-dione [Pindon] N-(4-chloro-2-methylphenyl)-N,N-dimethylformami' dine(Chlorphenamidin) 4-chlorobenzyl-4-fluorophenyl-sulphide side)5,6-dichloro-1-phenoxycarbanyl-Z-trifluoromethylbenzimidazole(Fenozaflor) p-chlorophenyl-p-chlorobenzenesulphonate (Ovex)p-chlorophenyl-benzenesulphonate (Fenson)p-chlorophenyl-2,4,5-trichlorophenylsulphone radifon)p-chlorophenyl-2,4,5-trichlorophenylsulphide (Tetrasul)p-chlorobenzyl-p-chlorophenylsulphide side)2-thio-l,3-dithiolo-(,5-6)-quinoxalir1e (Thiochinox)prop-2-ynyl-(4-t-butylphenoxy)-cyclohexysulphite (Propargil). v

(Fluorben- (Tet- (Chlorben- Furthermore, the new compounds of formula Ipossess extraordinarily good nematicidal properties, and can be used,for example,.for the control of the following plant-parasitic nematodes:Meloidogyne spp., Heterodera spp., Ditylenchus spp., Pratylenchus spp.,Paratylenchus spp., Anguina spp., Helicotylenchus spp.,Ty1enchlorhynclzus spp., Rotylenchulus spp., Tylenchulus semipentrans,Radopholus similus,, Belonolaismus spp., Trichodorus spp., Longia'orusspp., Aphelenchoides spp., Xyphinema spp..

In addition to possessing the above mentioned properties, the compoundsof formula I exhibit, applied in very small amounts, a favourable degreeof effectiveness against members of the class Thallophyta.

Thus, some of these compounds have a bactericidal action. They are,however, particularly effective against fungi, especially against thephytopathogenic fungi belonging to the following classes, orders orspecles.

such as Plasmodiphora-species, Aphanomyces-species, Pythium-species,Phytophthorn-species, e.g. (Phytophthora infestans, Phytophthoracactorum, Plasmopara-species, e.g. (Plasmopara viticola), Bremia-species(Bremia lactucae), Peronospora-species, e.g. (Peronospora tabacina),Pseudo-peranospora-species, e.g. (Pseudoperonospora humuli).

Zygomycetes, such as Rhizopus-species.

Ascomycetes, such as Eurotiales, such as Aspergillusspecies,Penicillium-species, e.g. (Penicillium digitatum, Penicillium italicum),

Taphrinales, such as Taphrina-species, e.g. (Taphrina deformans),

Erysiphales, such as Erysiphes-species, e.g. (Erysiphes Cichoracearum,Erysiphes graminis), Podosphaera Ieucotricha, Sphaerotheca-species(Spherotheca pannosa), Uncinula-species (Uncinula necator),

Helotiales, such as Monilinia-species (Manilinia [Sclerotinia]fructicola, Monilinia laxa), Diplocarponspecies (Diplocarpon rosae),Pseudopeziza-species,

Sphaeriales, such as Netria-species (Neczria galligena),

Ceratocystis-species,

Pseudosphaeriales, such as Venturia-species, (Venturia inaequalis),Mycosphaerella-species, phi0b0lusspecies (Ophiobolus graminis),Cochliobolus-species ([Helminthosporium] miyabeanus), Cercosporaspecies(Cercospora beticola, Cercospora musae).

Basidiomycetes, such as Aphyllophorales, Pelliculariaspecies, e.g.(Pellicularia filamentora [Rhizoctonia solam'1), Uredinales such asPucccinia-species, e.g. (Puccinia triticina), Uromyces-species (Uromycesphaseoli), Hemileia-species (Hemileia vastatrix), Cronartium-series(Cronarthium ribicola), Phragmidium-species (Phragmidium subcorticium),Gymnasporangium species.

Denteromycetes (Fungi impertecti) such as Piricu- [aria-species, e.g.(Piricularia oryzae), Corynesporaspecies, Thielaviopsis-species.Clasterosporiumspecies, Botrytis-species (Botrytis cinerea),Cladosporium-species, Alzernaria-species (Altern'aria solani),VerticiIlium-species (Verticillium alboatrum), Phialophora-species,Melanconiales, such as Colletotrichum-species, Fusarium-species, such as(Fusarium oxysporum, Fusarium nivale), Gloesporium-species (Gloesporiumfruchtigenum), Sphaeropsidales, e.g. Septoria-species (Septoriaapicola), Diplodia-species (Diplodia natalensis), Mycelia sterilia, e.g.Sclerotium series (Sclerotium rolfsii).

The compounds of formula I likewise have a fungitoxic action in the caseof fungi which attack the plants from the soil and cause, in some cases,tracheomycose, such as, e.g. F usarium cubense, Fusarium dianthi,Verticillium alboatrum and Phjalophora cinere'ceus.

Moreover, the new active substances can be used for the treatment ofseeds, fruit, tubers, etc., for the protection against fungusinfections, e.g. as a result of smut fungi of all kinds, such as:

Ustilaginales .such as Ustilaga-species (Ustilago avenae),Tilletia-species (Tilletia tritici), Urocystisand Tuburcinia-species,Phoma-species (Phoma betae).

By virtue of their biocidal properties, the compounds of formula I aresuitable for disinfection, and for the protection of diverse materialsagaint infestation by bacteria and fungi. It is shown to be in thisrespect particularly advantageous that the compounds of formula I, inconcentration such as are required for disinfection and for theprotection of materials, have no toxic side effects in the case ofwarm-blooded animals.

The compounds of formula I can be mixed, besides with the mentionedinsecticides and acaricides, with other fungicides, fungistitica orbacteriostatica in various mixture ratios, the compound mixtures thusobtained having advantages compared with the individual constituents.The following are, for example, suitable for being made up with theactive substance of formula I.

dodecylguanidineacetate (DODINE),

8 pentachloronitrobenzene (QUINTOZENE), pentachlorophenol (PCP),

2-( l-methyl-n-propyl )-4,6-dinitrophenyl-2- methylcrotonate(BINAPACRYL),

2-( lmethyl-n-heptyl-4,6-dinitrophenylcrotonate (DINOCAP),

2,6-dichloro-4-nitroaniline (DICHLORAN),

2,3,5,6-tetrachlorobenzoquinone 1,4)

ANIL),

2,3-dichloronapthoquinone (1,4) DICHLONE),

N-(Trichloromethylthio)-phthalimide (FOLPET),

N-(trichloromethylthio)cyclohex-4-ene-l ,2-

dicarboximide (CAPTAN),

N-( 1,l,2,2-tetrachloroethylthio)cyclohex-4-ene-1,2-

dicarboximide (CAPTAFOL),

N-methanesulphonal-N-trichloromethylthiochloroaniline,

N-dichlorofluoromethylthio-N-dimethyl-n'- phenylsulphamide(DICHLORFLUAMID),

O-ethyl-S-benzyl-phenyldithiophosphate,

0,0-diethyl-S-benzyl-thiolphosphate,

disodium-ethylene-l ,2-bis-dithiocarbamate (NABAM),

zinc-ethylene-1,2-bis-dithiocarbamate ZIN EB manganese (ll )-ethylene-l,Z-bis-dithiocarbam ate MANEB) tetamethylthiuramdisulphide THIRAM)l-oxy-3-acetyl-6-methylcyclohexene-( 5 )dione-( 2,4)

(DEHYDROACETIC ACID),

8-hydrooxyquinilone (8-QUINOLINOL),

Z-dimethylamino-6-methyl-5-n-butyl-4- hydroxypyrimidine,

methyl-N-benzimidazol-2-yl-N-(butylcarbamoyl)carbamate (BENOMYL),

2-ethylamino-6-methyl-5n-butyl-4-hydroxypyrimidine,

2,3-dicyano-l ,4-dithia-anthraquinone (DlTHlA NON2-(4-thiazolyl)-benzimidazole,

3,5-dimethyltetrahydro-1,3 ,5-thiadiazine-2-thione (DAZOMET),2,3-dihydro-S-carboxanilido-6-methyl-l ,4-oxathine, pentachlorobenzylalcohol.

CHLOR- The compounds of formula I can be used on their .own or togetherwith suitable carriers and/or additives. Suitable carriers and additivesmay be solid or liquid, and correspond to the substances common informulation practice, such as, e.g. natural and regenerated substances,solvents, dispersing agents, wetting agents, adhesives, thickeners,binders and/or fertilisers.

For application, the compounds of formula (I) can be processed into theform of dusts, emulsion concentrates, granulates, dispersions, sprays,solutions or suspensions, the formulation of these preparations beingeffected in a manner commonly known in practice. Also to be mentionedare cattle dips and spray races, in which aqueous preparations are used.

For the control of pests present in the soil, the new active substancesare applied in the form of solid or liq- :uid agents. For application tothe soil, such agents are particularly advantageous which ensure auniform distribution of the active substances through a layer of soilextending to a dpeth of 15 to 25 cm. The mode of application and theform of application are governed, in particular, by the type of soilpests to be controlled, by the climate, and by the conditions of thesoil. Since the new active substances are not phytotoxic and do notimpair germination power, they may be used, without the observance of awaiting period, directly before or after the sowing of the plants. It islikewise possible to treat already existing plant cultivations with thenew agents. Furthermore, the active substances can be applied just tothe parts of the plants above the soil.

The agents according to the invention are produced in a manner known perse by the intimate mixing and- /or grinding of active substances offormula I with the suitable carriers, optionally with the addition ofdispersing agents or solvents which are inert to the active substances.The active substances can be obtained and used in the followingpreparation forms:

solid preparations:

dusts, scattering agents, granulates,

coated granulates, impregnated granulates and homogeneous granulates;

liquid preparations: a) water-dispcrsihle active substance concentrates:wettable powders, pastes,

emulsions; h) solutions.

The solid preparations (dusts, scattering agents) are produced by themixing of the active substances with solid carriers. Suitable carriersare, e.g. kaolin, talcum, bole, loess, chalk, limestone, groundlimestone, Attaclay, dolomite, diatomaeeous earth, precipitated silicicacid, alkaline-earth silicates, sodium and potassium aluminum silicates(feldspar and mica), calcium and magnesium sulphates, magnesium oxide,ground synthetic materials, fertilisers such as ammonium sulphate,ammonium phosphate, ammonium nitrate, urea, ground vegetable productssuch as bran, bark dust, sawdust, ground nutshells, cellulose powder,residues of plant extractions, active charcoal, etc., alone or inadmixture with each other.

Granulates can be very easily produced by dissolving an active substanceof formula I in an organic solvent,

applying the thus obtained solution to a granulated mineral, e.g.attapulgite, SiO granicalcium, bentonite, etc., and then evaporating offthe organic solvent.

It is also possible to produce polymer granulates by the mixing of theactive substances of formula I with polymerisable compounds(urea/formaldehyde; dicyanodiamide/formaldehyde, melamine/formaldehydeor others), and the carrying out then of a careful polymerisation, bywhich process the active substances remain unaffected, and wherebygranulation is undertaken during gel formation. It is more favourable toimpregnate finished porous polymer granulates (urea/formaldehyde,polyacrylonitrile, polyesters and others) having a specific surface anda favourable predeterminable adsorption/desorption ratio, theimpregnation being effected with the active substances, e.g. in the formof their solutions (in a low boiling solvent), and the solvent thenremoved. Such polymer granulates can also be spread, in the form ofmicrogranules having a bulk weight of preferably 300 g/litre to 600g/litre, with the aid of powder Sprayers. The spraying can be carriedout over extensive areas of useful plant cultivations by means ofaeroplanes.

Granulates are also obtainable by compacting of the carrier materialwith the active substances and the additives, and subsequent grinding.

To these mixtures can also be added additives stabilising the activesubstance, and/or non-ionic, anionactive and cation-active substanceswhich, for example, improve the adhesiveness of the active substances onplants and parts of plants (adhesives and agglutinants),

propylene oxide, polyvinylpyrrolidones, polyvinyl alcohols, condensationproducts of urea/formaldehyde, as well as latex products.

Water-dispersible concentrates of active substances. i.e. wettablepowders, pastes and emulsion concentrates, are agents which can bediluted with water to obtain any desired concentration. They consist ofactive substance, carrier, optionally additives which stabilise theactive substance, surface-active substances. and anti-foam agents and,optionally, solvents,

The wettable powders and pastes are obtained by the mixing and grindingof the active substances with dispersing agents and pulverulentcarriers, in suitable devices, until homogeneity is obtained. Suitablecarriers are, e.g. those previously mentioned in the case of solidpreparations. It is advantageous in some cases to use mixtures ofdifferent carriers. As dispersing agents it is possible to use, e.g.:condensation products of sulphonated naphthalene and sulphonatednaphthalene derivatives with formaldehyde, condensation products ofnaphthalene or of naphthalene sulphonic acids with phenol andformaldehyde, as well as alkali, ammonium and alkaline-earth metal saltsof ligninsulphonic acid, also alkylarylsulphonates, alkali metal saltsand alkaline-earth metal salts of dibutylnaphthalenesulphonic acid,fatty alcohol sulphates such as salts of sulphated hexadecanols,heptadecanols, octadecanols, and salts of sulphated fatty alcohol glycolether, the sodium salt of oleyl methyl tauride, ditertiary ethyleneglycols, dialkyl dilauryl ammonium chloride, and fatty acid alkali metaland alkaline-earth metal salts.

Suitable anti-foam agents are, e.g. silicones.

The active substances are so mixed, ground, sieved and strained with theabove mentioned additives that the solid constituent in the case ofwettable powders has a particle size not exceeding 0.02 to 0.04 mm, andin the case of pastes not exceeding 0.03 mm. For the preparation ofemulsion concentrates and pastes, dispersing agents are used such asthose mentioned in the preceding paragraphs, organic solvents and water.Suitable solvents are, e.g. alcohols, benzene, xylene, toluene,dimethylsulphoxide, and mineral oil fractions boiling in the range of to350C. The solvents must be practically odourless, non-phytotoxic, andinert to the active substances.

Furthermore, the agents according to the invention can be used in theform of solutions. For this purpose, the active substance (or severalactive substances) of the general formula I is (or are) dissolved insuitable organic solvents, solvent mixtures, or water. As organicsolvents it is possible to use aliphatic and aromatic hydrocarbons,their chlorinated derivatives, alkylnaph-' thalenes, mineral oils ontheir own or in admixture with. each other.

The content of active substance in the above described agents is betweenO.l and 95 percent; it is to be mentioned in this connection that in thecase of appli-. cation of the agents from an aeroplane, or by means of}some other suitable application devices, concentrations} of up to 99.5percent can be used, or even the pure active substance itself.

The active substances of formula I can be prepared eg as follows:

Dusts The following substances are used for the preparation of a) adust, and b) a 2% dust:

5 parts of active substance, 95 parts of talcum.

2 parts of active substance,

1 part of highly dispersed silicic acid, 97 parts of talcum.

The active substances are mixed and ground with the carriers.

The following substances are used to produce a 5 granulate:

parts of active substance parts of epichlorhydrin,

parts of cetyl pol glycol ether,

parts of Eolyethy ene glycol,

parts of aolin (particle size 0.3 0.8 mm).

--wOOu| Outta Wettable powder The following constituents are used forthe preparation of a) a 40%, b) and c) a 25%, and d) a 10% wettablepowder:

a) parts of active substance,

parts of sodium lignin sulphonate,

part of sodium dibutyl-naphthalene sulphonate, parts of silicic acid.

parts of active substance,

parts of calcium lignin sulphonate parts of Champagne chalk/hydroxyethylcellulose mixture (1:1), 1

parts of sodium dibutyl naphthalene sulphonate, parts of silicic acid,

parts ofiCltampagne chalk, parts of kaolin.

parts of active substance,

parts of isooctylphenoxy-polyoxyethylene-ethanol, parts of Champagnechalk/hydroxyethyl cellulose mixture 1:1

parts of sodium aluminium silicate,

parts of kieselguhr,

parts of kaolin.

parts of active substance,

parts of a mixture of the sodium salts of saturated fatty alcoholsulphates,

parts of naphthalenesulphonic acid/formaldehyde condensate,

parts of kaolin.

ill U) Lil The active substances are intimately mixed, in suitablemixers, with the additives, the mixture being then ground in theappropriate mills and rollers. Wettable powders are obtained which canbe diluted with water to give suspensions of any desired concentration.

Emulsifiable concentrates The following substances are used to producea) a 10% and b) a 25% emulsifiable concentrate:

From these concentrates it is possible to produce, by dilution withwater, emulsions of any desired concentration.

Spray The following constituents are used to prepare a 5% spray:

5 parts of active substance, 1 part of epichlorhydrin, 94 parts ofbenzine (boiling limits ll90C).

EXAMPLE 1 a. A solution of 30.6 g of potassium hydroxide in 500 ml ofwater is added dropwise at 5l0, with stirring, to a mixture of 423 g of2,2-dimethylpropanal, 556.5 g of formalin and 900 ml of water. Stirringis continued overnight, and the reaction mixture is subsequentlyrepeatedly extracted with diethyl ether. The organic phases are dried,the solvent evaporated, and the residue fractionated in vacuo. Theobtained 3-hydroxy-2,2- dimethylpropanal (cp. CA. 65, l3529e (1966))boils at 86-9l/l3 Torr.

b. A solution of 82.5 g of sodium carbonate in 260 ml of water is addeddropwise at room temperature, with stirring, to a mixture of 108 g ofhydroxylamine hydrochloride, 132 g of 3-hydroxy-2,Z-dimethylpropanal and260 ml of water. The reaction mixture is refluxed for 3 hours, andsubsequently extracted with diethyl ether. The organic phase is driedand the solvent evaporated. The obtained3-hydroxy-2,2-dimethylpropanal-oxime is further reacted withoutpurification.

c. 350 ml of absolute diethyl ether and 350 ml of absolute benzene aremixed, and 117 g of 3-hydroxy-2,2-

6O dimethylpropanal-oxime dissolved therein. To this so- ...ms hxusrstsl 119 999. whi h m lt2t 9TF d. A solution of 51.4 g ofethylsulphochloride in 50 ml of absolute benzene is added at roomtemperature, with stirring and within one hour, to a solution of 69.6 gof 3-hydroxy-2,2dimethylpropanal-(N'- rnethylctirbnmoyl l-oximc and 40.4g of triethylamine in mm ml of absolute benzene. Stirring is continuedfor a further hour at room temperature, and subsequently for 2 Va hmiriiwith refluxing. After cooling. the reaction mixture iii washed withwater and diluted hydrochloric acid, the organic phase ill then driedand the solvent evaporated off. The residue is washed with 100 ml ofcold diethyl ether. Thus obtained is 3-(ethylsulphonyloxy)-2,2-dimethylpropanal-(N- methylcarbamoyll-oximc.M.P.: 52-53.

The following compounds too are produced in an analogous manner:

period of 8 days.

The galls present on the roots are counted 28 days after planting andafter sowing, the results being then used as a basis for the assessmentof the nematocidal action.

= full nematocidal action no infestation. no nematocidal action the sameinfestation as in the case of the control test, l-4 intermediate stagesof infestation.

Evaluation Test series A (Table l) Nematocidal action Active substance50 ppm ppm 3-( Methyl-sulfonyl-oxy)-2,2 dimethyl-propanal- 2(N-mcthylcarbamoyl)-oximc 3-(Ethyl-sulfonyl-oxy)-2,2-dimethyl-propanall2 (N-methylcarbam0yl)-oxime 3-(Chlormethylsulfonyl-oxy)-2,2-dimethyl-propanal- 0 2 (N'-mcthylcarbamoyl)-oximcTetrahydro-3,S-dimethyl-ZH-l ,3,5-thiadiazine-2-thione 5 5 (known fromChem. Week No. [2.4.69, p. 56)

Test series B (Table 2) Active substance Nematocidal action 50 ppm 10ppm 3-(Methyl-sulfonyl-oxy)-2,2-dimethyl-propanal- 0 (N-methylcarbamoyl)-oxime 3-(Ethylsulfonyl-oxy)-2,2-dimethyl-pr0panal- 0 0(N-mcthylcarbamoyl )-oxime3-(Chlormethyl-sulfonyl-oxy)-2,2-dimethyl-propanal- O l(N'-methylcarbamoylJ-oxime Tetrahydro-3,S-dimethyl-ZH- l,3,5-thiadiazine-2-thione 3 5 (known from Chem. Week No. l2.4.69, p. 56)

MP. "C

3-(4'-methylphen lsulphonyloxy)-2,2-dimcthyl-3-(ethdyxlsulphonyloxy)'2,2-dimethyl-propanal- (N'-e ylcarbamoylroxime3-(chloromethylsulphonyloxy )-2,2-dimethylipropanal-(N'-ethylcarbamoyl)-oxime EXAMPLE 2 Nematocidal test To testthe action against soil nematodes, the active substance is added, in thestated concentration, to soil infested by root-gall nematodes(Meloidogyne arena ria), and the whole intimately mixed. In the test scEXAMPLE 3 Action Against Ticks A. Rhipicephalys bursa Small glass tubeseach contain either 5 adult ticks or tick larvae and the glass tubes areimmersed for l or 2 minutes in 2 ml of an aqueous emulsion from adiilLlIlOl'l series comprising dilutions of 100, 10, l, and 0.1 ppm oftest substance. The glass tube is then closed with a standardised cottonplug and inverted, so that the active substance emulsion can be absorbedby the cotton wool.

The assessment of the results in the case of the adults is made after 2weeks, and in the case of the larvae after 2 days. Two repeats of eachtest are made.

B. Boophilus microplus (Larvae) With a dilution series analogous to thatin test A, tests are carried out using in each case 20 larvae sensitiveto OP and 20 OP-resistant larvae (The resistance relates to thecompatibility with respect to Diazinon). The compounds according toExample l exhibit in these tests a good degree of effectiveness againstadults and larvae of Rhipicephalus bursa, and against larvae of B0-pphjlusr nicroplus.

EXAMPLE 4 Acaricidal action An infested piece of leaf from a massculture of Terranychus urn'cae is placed, 12 hours before the test, ontoPhaseolus vulgaris (kidney beans). The transferred mobile stages aresprayed from a chromatography sprayer with the emulsified testpreparations, this being effected without any running down of the sprayemulsion. Larvae, adults and eggs are examined under a binocular aftertwo to seven days in order to assess the number of living forms and deadforms, the result being then expressed as percentages. During theholding time," the treated plants are kept in greenhouse compartments at25C.

The compounds according to Example 1 have an excellent action in theabove test against adults, larvae and eggs of Tetranychus urticae.

EXAMPLE 5 lnsecticidal stomach poison action Tobacco and potato plantsare sprayed with a 0.05% aqueous active substance emulsion (obtainedfrom a emulsifiable concentrate).

After the drying of the coating, Egyptian cotton-leaf worms (Spudopleralitoralis) are placed onto the tobacco plants, and Colorada beetlelarvae (Leptinotarsa decemlineata) onto the potato plants. The test isperformed at 24 with 60 percent relative humidity. Systemic insecticidalaction To establish the systemic action, rooted bean plants (Viciafabae) are placed into a 0.01% aqueous active substance solution(obtained from a 10% emulsifiable concentrate). After 24 hours, aphids(Aphis fabae) are placed on the parts of the plants above the soil. Theinsects are protected by a special device from the effect of contact andof gas. The test is carried out at 24 with 70% relative humidity.

The compounds according to Example 1 display in the above tests a goodinsecticidal stomach poison action and systemic insecticidal action.

EXAMPLE 6 Fungicidal action a. Action against Botrytis cinerea on Viciafaba In Petri dishes lined with moistened filter paper were placed, ineach dish, three fully developed and equally large Vicia faba leaves,these having been sprayed with a spraying apparatus until dripping wetwith a solution (0.1% active substance content) prepared with the activesubstance made up as a 10% wettable powder. When the leaves were againdry, they were infected with a freshly prepared standardised sporesuspension of the fungus (concentration: 100,000 spores/ml), and keptfor 48 hours in a moist atmosphere at C. The leaves displayed after thisperiod of time black, initially point-like spots, which rapidly spread.The number and size of the infection points served as a criterion inassessing the effectiveness of the test substance.

b. Action against Erysiphe cichoracearus on Cucumis satz'vus After beingsprayed with a 0.1% suspension of the active substance prepared as awettable powder, and after the drying of the sprayed-on coating, youngCucumis sativus plants were sprayed with a spore suspension of thefungus. After the plants had been in a greenhouse for 8 days at ca. 23C,an assessment was made of the Lil degree of infection (proportion onleafsurl'aee covered with the mycelium) on the infected treated leavesin comparison with that present on the untreated infected controlspecimens.

0. Action against Uromyccsappendiculartci' on llluxt'o [us vulgariaPhaseolus vulgaris plants in the two-leaf stage were sprayed drippingwet with a suspension of the active substance (conc.: 0.1% of activesubstance) made up as a wettable powder. After the drying of thesprayedon coating, the plants were infected with a fresh sporesuspension of bean rust, and subsequently kept for one day in a moistchamber, and then for 12 days in a greenhouse at 20 22C.

The number and size of the rust spots served as a criterion in theassessment of the effectiveness of the test substances.

d. Action against Phytophthora infestans on Solanum Lycopersicum S.Lycopersicum plants of the same type and in the same development stagewere sprayed in the dry state, after having been previously sprayed witha solution of 0.1% of active substance (produced from the activesubstance in the form of a wettable powder), with a zoosporesuspensionof Ph. infestans until dripping wet. The plants then remained for 6 daysin a greenhouse at 18 -20C with high humidity (95-100 percent), and weredisplaying after this period of time typical leaf spots. The assessmentof the tested substance was made on the basis of the number and size ofthe spots.

e. Action against Podesplzaera Ieucotric/za (Ell.et Ev.) Salm on smallapple trees Apple-cuttings of the type MM 1 11 were grown during thetest in a greenhouse at 20C with relative humidity. When 3 to 4 leaveshad unfolded on each of the developing lateral shoots, the leaves weresprayed dripping wet with a spray solution prepared from the activesubstance made up as a 10% wettable powder (solution: 0.1% activesubstance content). After the drying of the sprayed-on coating, theleaves were evenly sprayed on the upper side with a spore-solution ofthe fungus.

The small apple trees were again sprayed with the above described activesubstance preparation at intervals of 7 and 14 days after the initialtreatment. The evaluation of the test results was made 12 days after thelast treatment.

The assessment of the effectiveness of the test substance was made onthe basis of the number and size of the p9 ntsa flnfssti f. Actionagainst Plasmopara viticola (Bert. et Curt.) (Berl. et DeToni) ongrape-vines Grape-vine cuttings of the type Chasselas" were grown in.agreenhouse. In the l0-leaf stage, 3 plants were sprayed dripping wetwith a spray solution of the active substance formulated as a 10%wettable powder (0.1% active substance content of the solution). Afterthe drying of the sprayed-on coating, the plants were uniformly infectedon the underside of the leaves with the spore-suspension of the fungus.The plants were subsequently kept for 8 days in a moist chamber. Therewere signs of infection on the control plants after this period of time.The assessment of the effectiveness of the test substance was made onthe basis of the number and size of the areas of infection.

the formula g. Action against Septoria apicola Spegaizfni on Celeryplants Celery of the type Challon was grown in a greenhouse. The youngplants, each fifteen centimetres high, were sprayed until dripping wetwith a spray solution (0.1% active substance content) prepared from theactive substance made up as a wettable powder. After the drying of thesprayed-on coating, the plants were infected with a sporesuspension ofthe fungus. After 2 days in a moist chamber, and 12 days at -22C with 90percent relative humidity in a green house, symtoms of infectionappeared. The number and size of the points of infection serves as acriterion in the assessment of the effectiveness of the test substance.

h. Action against Erysiphe graminis DC. on Triticum In a greenhouse at20C, young wheat plants approximately 10 cm in length were sprayeddripping wet with a spray solution (0.1% active substance content)prepared from the active substance made up as a 10% wettable powder.After the drying of the sprayed-on coat ing, the plants were infectedwith conidia of the fungus. The percentage infestation of the plants wasdeter mined after 12 days (greenhouse 20C).

i. Action against Puccinia triticina Eritess on Triticum In a greenhouseat 20C, young wheat plants approximately 10 cm in length were sprayeduntil dripping wet with a spray solution (01% active substance content)prepared from the active substance made up as a 10% wettable powder.After the drying of the sprayed-on coating, the plants were uniformlyinfected with a uredospore suspension of the fungus. After 5 days in ahumid chamber and 12 days in a greenhouse at 20-22C with normal relativehumidity, an assessment of the test results was made. The number andsize of the points of infection served as a criterion in the assessmentof the effectiveness of the test substance.

The compounds according to Example 1 exhibited in the above tests a) toi) a good fungicidal action.

l claim:

1. A method for combatting phytophathogenic fungi which comprisesapplying to an area infested with said fungi a fungicidally effectiveamount of a compound of wherein R represents C -C alkyl, C -C haloalkyl,C -C alkenyl or phenyl optionally substituted by halogen, nitro or C Calkyl, and R represents C -C alkyl.

2. The method according to claim 1 in which R represents methyl,chloromethyl, ethyl, n-propyl, n-butyl, 3,3,3-trichl0ropropenyl,4-methylphenyl or 2,4,5- trichlorophenyl, and R represents methyl orethyl.

3. The method according to claim 2 in which R, represents chloromethyl,ethyl or n-propyl.

4. The method of claim 3 in which the compound is3-(ethylsulphonyloxy)-2,2-dimethyl-propanal-(N'- methylcarbamoyl)-oxime.

5. The method of claim 2 in which the compound is3-(4-methylphenylsulphonyloxy)-2,2-dimethylpropanol-(N-methylcarbamoyl)-oxime.

6. The method of claim 2 in which the compound is3-(methylsulphonyloxy)-2,2-dimethyl-propanal-N'- methylcarbamoyl)-oxime.

7. The method of claim 3 in which the compound is3-(chloromethylsulphonyloxy)-2,2-dimethyl-propanal- (N '-methylcarbamoyloxime.

8. The method of claim 2 in which the compound is3-(2',4',5-trichlorophenylsulphonyloxy)-2,2-dimethyl-propanal-(N-methylcarbamoyl)-oxime.

9. The method of claim 2 in which the compound is3-(3,3,3-trichloropropenesulphonyloxy)-2,2-dimethyl-propanal-(N-methylcarbamoyl)-oxime.

10. The method of claim 3 in which the compound is3-(n-propylsulphonyloxy)-2,2-dimethyl-propanal-(N'-methylcarbamoyl)-oxime.

11. The method of claim 2 in which the compound is3-(n-butylsulphonyloxy)-2,2-dimethyl-propanol-( N methylcarbamoylyoxime.

12. The method of claim 3 in which the compound is3-(ethylsulphonyloxy)-2,2-dimethyl-propanal-(N'- ethylcarbamoyl)-oxime.

13. The method of claim 3 in which the compound is3-(chloromethylsulphonyloxy)-2,2-dimethylpropanal-(N-ethylcarbamoyl)-oxime.

1. A METHOD FOR COMBATTING PHYTOPHATHOGENIC FUNGI WHICH COMPRISESAPPLYING TO AN AREA INFESTED WITH SAID FUNGI A FUNGICIDALLY EFFECTIVEAMOUNT OF A COMPOUND OF THE FORMULA
 2. The method according to claim 1in which R1 represents methyl, chloromethyl, ethyl, n-propyl, n-butyl,3,3,3-trichloropropenyl, 4-methylphenyl or 2,4,5-trichlorophenyl, and R2represents methyl or ethyl.
 3. The method according to claim 2 in whichR1 represents chloromethyl, ethyl or n-propyl.
 4. The method of claim 3in which the compound is3-(ethylsulphonyloxy)-2,2-dimethyl-propanal-(N''-methylcarbamoyl)-oxime.5. The method of claim 2 in which the compound is3-(4''-methylphenylsulphonyloxy)-2,2-dimethyl-propanol-(N''-methylcarbamoyl)-oxime.
 6. The method of claim 2 in which the compound is3-(methylsulphonyloxy)-2,2-dimethyl-propanal-N''-methylcarbamoyl)-oxime.7. The method of claim 3 in which the compound is3-(chloromethylsulphonyloxy)-2,2-dimethyl-propanal-(N''-methylcarbamoyl)-oxime.
 8. The method of claim 2 in which the compound is3-(2'',4'',5''-trichlorophenylsulphonyloxy)-2,2-dimethyl-propanal-(N''-methylcarbamoyl)-oxime.
 9. The method of claim 2 in which the compoundis3-(3'',3'',3''-trichloropropenesulphonyloxy)-2,2-dimethyl-propanal-(N''-methylcarbamoyl)-oxime.
 10. The method of claim 3 in which the compoundis3-(n-propylsulphonyloxy)-2,2-dimethyl-propanal-(N''-methylcarbamoyl)-oxime.11. The method of claim 2 in which the compound is3-(n-butylsulphonyloxy)-2,2-dimethyl-propanol-(N''-methylcarbamoyl)-oxime.12. The method of claim 3 in which the compound is3-(ethylsulphonyloxy)-2,2-dimethyl-propanal-(N''-ethylcarbamoyl)-oxime.13. The method of claim 3 in which the compound is3-(chloromethylsulphonyloxy)-2,2-dimethyl-propanal-(N''-ethylcarbamoyl)-oxime.